EP0268849A2 - Blocage de polyols à l'aide d'amines aromatiques - Google Patents

Blocage de polyols à l'aide d'amines aromatiques Download PDF

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EP0268849A2
EP0268849A2 EP87115677A EP87115677A EP0268849A2 EP 0268849 A2 EP0268849 A2 EP 0268849A2 EP 87115677 A EP87115677 A EP 87115677A EP 87115677 A EP87115677 A EP 87115677A EP 0268849 A2 EP0268849 A2 EP 0268849A2
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residue
groups
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poly
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EP0268849A3 (en
EP0268849B1 (fr
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Visweswara R. Durvasula
Fred A. Stuber
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Dow Chemical Co
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Dow Chemical Co
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
    • C08G65/322—Polymers modified by chemical after-treatment with inorganic compounds containing hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
    • C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
    • C08G18/5027—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups directly linked to carbocyclic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5072—Polyethers having heteroatoms other than oxygen containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/52—Polythioethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
    • C08G65/33379—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing nitro group
    • C08G65/33386—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing nitro group cyclic
    • C08G65/33389—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing nitro group cyclic aromatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/48—Polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers

Definitions

  • This invention relates to the preparation of high molecular weight aromatic polyamines and is more particu­larly concerned with aromatic amine capped polyols or polythiols, the nitroaromatic precursors therefor, and the novel polyisocyanate polyaddition products derived from said polyamines.
  • Aliphatic based polyamines as typically disclosed in U. S. Patents 3,436,359, 3,654,370, and 3,847,992 are possessed of very high reactivity rates in polyaddition polymerizations with polyisocyanates.
  • the polyamino compounds react almost instantaneously and to overcome the problem the polyamines are employed in the form of their salts as taught in U. S. 3,256,213.
  • the latter patent includes aromatic amine compounds also but neglects to show their much slower reactivities compared with the reference's principal aliphatic polyamines.
  • aromatic amine compounds are just the opposite tending to be sluggish in their reactivity with polyisocyanates.
  • Typical of aromatic amines are those disclosed in U. S. Patents 2,888,439, 3,808,250, 4,129,741, 4,169,206, 4,328,322, 4,537,945, 4,609,683 and 4,609,684. These compounds have terminal aminophenyl groups linked to polyvalent residues through ester linkages, amide linkages, urethane linkages, and aromatic amido-aromatic ester linkages.
  • This invention is directed to poly(aminoaromatic) compounds and process therefor, said compounds character­ized by the formula wherein R is the residue after removal of hydroxyl groups or mercapto groups respectively of a polymeric polyol or polythiol having a molecular weight of from 400 to 10,000 and a functionality n of from 2 to 6, -X- represents -O- when said R is the residue of a polyol and -S- when said R is the residue of a polythiol, y is 1 or 2 and A is selected from hydrogen and an inert substituent.
  • This invention is also directed to poly(nitro­aromatic) precursor compounds (II) and process therefor which correspond to formula (I) above except for the appearance of the -NO2 groups in place of the -NH2 groups.
  • This invention is also directed to molded synthe­tic resins containing polyurea linkages and process there­for obtained from the reaction of (I) with organic poly­isocyanates, optionally in the presence of polymeric polyols and/or extenders.
  • This invention is also directed to films cast from solutions of the above described polyurea synthetic resins based on the poly(aminoaromatic) compounds of formula (I).
  • inert substituent means any substituent that does not react with an amine, nitro, or hydroxyl group and is inclusive of lower-alkyl of 1 to 8 carbon atoms, inclusive, such as methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, and isomeric forms thereof; aryl of 6 to 12 carbon atoms, inclusive such as phenyl, tolyl, naphthyl, and biphenylyl; aralkyl of 7 to 10 carbon atoms, inclusive, such as benzyl, and phenethyl; cycloalkyl of 4 to 6 carbon atoms, inclusive, such as cyclobutyl, cyclo­pentyl, and cyclohexyl; alkoxy of 1 to 8 carbon atoms, inclusive, such as methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy,
  • this novel class of polyamines defined by formula (I) is characterized by amine reac­tivities which, for the most part, are intermediate of the two classes of prior art polyamines described above. Addi­tionally, depending on the mode of substitution of the amine groups, the present polyamines can be provided with varying reactivies within the group.
  • the compounds of formula (I) can be used as co­-reactants and/or curatives with epoxy resins and in the formation of various types of polyaddition products with organic polyisocyanates.
  • Exemplary of such polyaddition products are polyureas, and polyurethane-polyureas.
  • the compounds of formula (II) can be used as solubilizing agents in combination with aqueous alkaline flooding media in the recovery of hydrocarbons from sub­terranean hydrocarbon-bearing formations. However, they find their prime utility as intermediates for the production of compounds of formula (I).
  • the compounds (I) are conventionally produced from the nitro precursors by reduction with base metals, e.g. tin or iron, in the presence of acids. Alternatively, they are obtained by the catalytic hydro­genation of the nitro groups using well known hydrogenation procedures. Obviously, the amino compounds may be prepared by any other known methods.
  • the products are produced by the catalytic hydrogenation method.
  • Catalytic Hydrogenation over Platium Metals Any of the catalysts known to be useful for the reduction of aromatic nitro groups can be employed inclusive of Raney nickel.
  • a preferred group of catalysts is comprised of the platinum group metals which includes ruthenium, rhodium, palladium, osmium, iridium, and platinum.
  • the catalyst is supported on a carrier such as activated carbon, silica gel, alumina, diatomaceous earth, and pumice. The exact proportions in which the elemental metal is present on the carrier is not a critical factor. Generally speaking, the metal can vary from 0.05 to 40 percent by weight, preferivelyably from 0.5 to 20, and, most preferably, from 5 to 10 percent by weight.
  • the proportions of catalyst employed expressed as the pure metal in respect of the nitro group to be reduced will advantageously fall within the range of from 0.05 to 10 mole percent of metal per equivalent of nitro group. Preferably, the range is 0.1 to 1.0 mole percent.
  • the term "equivalent of nitro group” means the nitro equivalent weight which is obtained by dividing the molecular weight of the nitroaromatic compound (II) by the number of nitro groups per mole.
  • the hydrogenation is conducted in the liquid phase in the presence of the hydrogen and the catalyst component which, generally speaking, calls for the use of a solvent but the latter is not absolutely necessary.
  • Any solvent known to be useful for catalytic hydrogenation methods but inert to the compounds (I) and (II) may be employed.
  • the following solvents can be used solely or as mixtures thereof: aromatic hydrocarbons such as benzene, toluene, and xylene; alcohols such as methanol, ethanol, propanol, and isopropanol; esters such as ethyl acetate, ethyl propionate, and ethyl butyrate; ethers such as dioxane, and tetrahydrofuran; and, water either alone or in combination with the above solvents.
  • the use of liquid ammonia is also contemplated.
  • the amount of solvent is not critical per se and any amount found to be efficacious can be employed.
  • the nitroaromatic compound (II) is employed in at least 10 percent by weight in the solvent, preferably, from 20 to 70 percent by weight, and, most preferably, 25 to 50 percent by weight.
  • temperature in any given hydrogenation is a function of the specific catalyst activity, and hydrogen pressure.
  • it can fall within a range of from 0°C to 200°C, preferably from 15°C to 100°C, most preferably 20°C to 50°C.
  • the hydrogen pressure employed can cover any effective range such as from 1 kg/cm2 up to any reasonable working pressure. Generally speaking the pressure will be from 1 kg/cm2 to 14 kg/cm2, preferably from 2 to 4 kg/cm2.
  • Isolation of the compound (I) is carried out using well known conventional procedures.
  • the catalyst is separated using standard methods of filtration and is readily recoverable either for direct recycling to another reduction or subjected to recovery steps prior to recycle.
  • Product separation is then achieved by removing solvent using distillation methods under atmospheric and/or reduced pressures.
  • the product is in the form of a mobile to viscous liquid. If further purification is necessary or desirable, it can be treated with adsorbents (i.e. charcoal) or passed through exchange resins.
  • adsorbents i.e. charcoal
  • the precursor nitroaromatic compound will contain some unreacted polyol or polythiol which will result in hydrogenated product mixtures which are not fully capped.
  • aminoaromatic product (I) will contain minor proportions of polyol or polythiol components.
  • such components are not in any way harmful to the ultimate utility of the compounds (I) and need not be separated from the product unless desired or necessary.
  • nitroaromatic compounds (II) In respect of the preparation of the nitroaromatic compounds (II), while the above schematic equation sets forth one embodiment therefor, it is not necessarily limited thereto. Any conventional method may be employed.
  • the appropriate alkali-nitrophenolate can be condensed with the appropriate polyhalogen terminated compound.
  • a polyol or polythiol (IV) having n hydroxyl or mercapto groups is reacted with at least n equivalent moles of the nitro halo-substituted benzene (III) in the presence of strong bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium methoxide, sodium ethoxide, and potassium methoxide in an inert solvent.
  • inert solvent means any solvent which does not react with any of the reactants or products nor otherwise interfere with the overall process.
  • Typical solvents include benzene, toluene, xylene, chlorobenzene, dichlorobenzene, and nitrobenzene; ethers such as tetrahydrofuran, and dioxane.
  • the reaction is carried out at 20°C to 200°C, preferably from 35°C to 100°C and for a period necessary to consume the reactants (III) and (IV).
  • Any convenient analytical method for determining the presence of these reactants can be employed to monitor the progress of the reaction. For example, thin layer chromatography, gel permeation chromatography, nuclear magnetic resonance, and infrared are useful methods.
  • nitrohalobenzenes (III) are 4-nitrochlorobenzene, 4-nitrobromobenzene, 4-nitrofluorobenzene, 4-nitroiodo­benzene, 2-nitrochlorobenzene, 2-nitrobromobenzene, 2-nitrofluorobenzene, 2-nitroiodobenzene, 3-nitrochloro­benzene, 4-nitro-3-methylchlorobenzene, 4-nitro-3-ethyl­chlorobenzene, 4-nitro-3-butylchlorobenzene, 4-nitro-3­-hexylchlorobenzene, 4-nitro-3-octylchlorobenzene, 2-nitro­-4-methylchlorobenzene, 2-nitro-4-ethylchlorobenzene, 2-nitro-4-butylchlorobenzene, 2-nitro-4-hexylchlorobenzene, 2-nitro-4-octylchlorobenzene
  • the novel polyamines (I) can be provided with varying reactivities in respect of the amine functions. It has been observed that this property depends primarily on the position of the amine group(s) on the aromatic ring and their number. Ortho- and para-­substitution provides the widest control of amine reactiv­ity particularly when y is equal to one. Accordingly, a preferable class of starting compounds (III) comprises those wherein the nitro group is in the ortho or para position relative to the halogen atom when y equals one or occupying both positions when y equals two. For the slowest amine activities, it is even more preferable that y equals one and the nitro group be in the ortho position. Thus, these same preferences apply to the formed poly­(nitroaromatic) compounds (II) and poly(aminoaromatic) compounds (I). It is further preferred that A be hydrogen.
  • the polyols or polythiols (IV) include any of the known polyols and polythioether polythiols and polythiols meeting the defined limits set forth above when describing the residue R.
  • Preferably (IV) is a polymeric polyol having a functionality n of from 2 to 4 and a molecular weight of from 1500 to 6000. Accordingly, these preferred limitations apply to the compounds (I) and (II) so that X is -O- and R is the residue of a polymeric polyol so described.
  • polystyrene resin examples include polyethylene glycols, polyethylene glycols, polyethylene glycols, polypropylene glycols, polyethylene glycols, polyethylene glycols, polystyrene resins, polystyrene resins, polystyrene resins, polystyrene resins, polystyrene resins, polystyrene resins, polystyrene resins, polysulfonate, polystyrenethacrylate, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene resinstyrene resinstyrene resinstyrene resins, polystyrene resinstyrene resinstyrene resinstyrene resins, polyst
  • polyols obtained by the polymerization of styrene or acrylonitrile in the presence of the polyether; polyacetals prepared from glycols such as diethylene glycol and formaldehyde; polycarbonates, for example those derived from butanediol with diarylcarbonates; polyester amides, the resole polyols (see Prep. Methods of Polymer Chem. by W. R. Sorenson et al., 1961, page 293, Interscience Publishers, New York, N.Y.); and the polybutadiene resins having primary hydroxyl groups (see Poly Bd. Liquid Resins, Product Bulletin BD-3, October 1974, Arco Chemical Company, Div. of Atlantic Richfield, New York, N.Y.).
  • a preferred group of polyols comprises the polyalkyleneoxy polyols free of sulfur, in particular polymers of ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran or polyether polyols which contain propylene oxide units alone or in combination with ethylene oxide in any sequence.
  • Polyols of this type are well known and, for the most part, are commercially available. Gener­ally speaking, they are easily prepared by polymerizing the desired alkylene oxide in the presence of a starter such as water, ethylene glycol, propylene glycol, aniline, glyc­erol, trimethyolpropane, pentaerythritol, methylglucoside, and mixtures thereof.
  • a preferred subclass of compounds according to formulae (I) and (II) in accordance with the present invention are those wherein -X- is -O-, R is the residue after removal of hydroxyl groups of a polymeric polyol having a molecular weight of from 1500 to 6000 and a functionality n of from 2 to 4, y is 1 and said NH2 or NO2 groups being in the ortho or para position relative to -O- and A is hydrogen.
  • the compound (I) can be the sole reactant with the polyisocyanate in which case the major recurring units are linked through polyurea linkages.
  • polymeric polyols of the type described above under (IV) can be employed in varying proportions and/or extenders.
  • polyurethane and/or additional urea linkages are also present.
  • an extender is employed in combination with (I).
  • the polyaddition is carried out in the presence of a low molecular weight extender of from about 62 to about 400.
  • a low molecular weight extender of from about 62 to about 400.
  • Typical of such extenders are ethylene glycol, 1,4-butanediol, 1,6-hexane­diol, 1,4-cyclohexanedimethanol, neopentyl glycol, bis(2­-hydroxyethyl)ethers of hydroquinone and resorcinol, hexa­methylene diamine, octamethylene diamine, 2,4-diamino­toluene, 2,6-diaminotoluene, 4,4 ⁇ -diamino-3,3 ⁇ -dichloro-­diphenylmethane, 2,4-diamino-3,5-diethyl toluene, 2,6­-diamino-3,5-diethyl tolu
  • the relative equivalent proportions of said extender per equivalent of said (I) advantageously falls within the range of 1:1 to 80:1, preferably, from 3:1 to 8:1.
  • the polyisocyanates employed can be any of the organic di- or higher functionality polyisocyanates known to be useful for such polyaddition product preparation.
  • the preferred class of polyisocyanates is that which comprises the aromatic polyisocyanates.
  • polyisocyanates but not limiting thereof are hexamethylenediisocyanate, iso­phoronediisocyanate, methylenebis(cyclohexyl isocyanate), m- and p-phenylene diisocyanate, 2,4- and 2,6-toluene diisocyanate and mixtures of these two isomers, methylene­bis(phenyl isocyanate) inclusive of 4,4 ⁇ -methylenebis­(phenyl isocyanate), 2,4 ⁇ -methylenebis(phenyl isocyanate), and mixtures of these methylenebis(phenyl isocyanate) isomers in any proportion, 3,3 ⁇ -dimethyl-4,4 ⁇ -diisocyanato-­diphenyl methane; polymethylene polyphenylisocyanate mix­tures comprising 20 to 80 percent methylenebis(phenyl isocyanate) with the remainder of the mixture being polyisocyanates of functionality greater than 2, lique
  • proportions of polyisocyanate to the total active hydrogen equivalents comprised of (I), any optional polymeric polyol, and extender are such that the ratio of isocyanate equivalents to total active hydrogen equivalents falls within a range of from 0.85:1 to 1.20:1, preferably from 0.95:1 to 1.10:1.
  • any of the urethane catalysts disclosed in the art can be employed.
  • Such catalysts include organic and inor­ganic acid salts of, and organometallic derivatives of bismuth, tin, lead, antimony, and cobalt.
  • a preferred group includes stannous octoate, stannous oleate, dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin maleate, dibutyltin mercaptopropion­ate, dibutyltin didodecylmercaptide, and dibutyltin bis(isooctyl thioglycolate); triethylamine, triethyl­enediamine, N,N,N ⁇ ,N ⁇ -tetramethylethylenediamine, N-methyl­morpholine, and N,N-dimethylcyclohexylamine; and mixtures of any of the above.
  • blowing agents may be employed for the formation of cellular micro-cellular, and self-skinned molded parts characterized by tough skinned surfaces.
  • Other optional additives include, illustratively, dispers­ing agents, cell stabilizers, surfactants, internal mold release agents, flame retardants, colorants, reinforcing agents, fiberglass roving and mats.
  • Typical of the molded synthetic resins formed by the present compounds are solid cast elastomers, solid and micro-cellular RIM elastomers and elastoplastics. Such products find utility as auto parts including bumpers, body elements, panels, doors, hoods, skirts, and air scoops.
  • Typical solvents are dipolar aprotic solvents such as dimethylformamide, dimethyl­acetamide, and dimethylsulfoxide; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ethers such as dioxane, and tetrahydrofuran.
  • dipolar aprotic solvents such as dimethylformamide, dimethyl­acetamide, and dimethylsulfoxide
  • ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone
  • ethers such as dioxane, and tetrahydrofuran.
  • the solutions can be used for coating compositions for wire coatings, casting or spraying of polymer films on a variety of substrates such as metal, ceramic, and fabrics.
  • a one-liter four-necked flask was equipped with a mechanical stirrer, reflux condenser, thermometer, and air inlet tube.
  • the flask was charged with 200 g. (0.1 mole) of a 2000 molecular weight polypropyleneoxy-polyethyleneoxy diol containing 12 percent by weight ethyleneoxy units, 20 g. (0.5 mole) of powdered sodium hydroxide and 400 ml. of toluene.
  • a very slow stream of air was maintained in the flask and after fifteen minutes, 31.5 g. (0.2 mole) of 2-nitrochlorobenzene dissolved in 100 ml. of toluene was added.
  • the resulting reaction mixture was stirred at room temperature for two hours during which time the temperature of the solution rose to 38°C and then returned to ambient (27°C).
  • the reaction mixture was heated at 65 to 70°C for 4 hours by means of an oil bath.
  • Thin layer chromatography (TLC) analysis using a silica gel plate and developing in a 23/2 (V/V) mixture of cyclohexane/ethyl acetate, showed that the majority of the 2-nitrochlorobenzene had reacted.
  • the reaction mixture was cooled to 10 to 15°C and acidified by adding 30 ml. of concentrated hydrochloric acid in 125 ml. of water and stirred until it turned to a light yellow color.
  • the mixture was transferred to a separatory funnel followed by washings from the flask consisting of 100 ml. of toluene and 15 ml. of water.
  • the relative reactivity of this di(aminoaromatic) compound relative to 4,4 ⁇ -methylenedianiline was measured by injecting simultaneously into an infrared cell 100 microliters of a 1.5 wt. percent solution of phenyliso­cyanate dissolved in dimethylsulfoxide and 100 microliters of an equivalent proportion of the diamine (13.9 wt. per­cent) in dimethylsulfoxide and observing the disappearance of the isocyanate band (2250 cm ⁇ 1) with time at ambient temperature (20 to 30°C).
  • the control methylenedianiline was assigned the value of unity (1) and the value for the di(aminoaromatic) compound was observed as 0.04.
  • the polypropyleneoxy-polyethyleneoxy diol was dissolved in 300 ml. of toluene followed by bubbling in air for five minutes. During stirring, 31.5 g. (0.2 mole) of 4-nitrochlorobenzene was added to the solution. After ten minutes, the 20 g. of sodium hydroxide was added followed by the remaining 100 ml. portion of toluene. Stirring was continued for approximately one hour at the solution temperature of 27 to 28°C. TLC analysis of an aliquot sample showed no reaction had occurred. The solution was heated at 62 to 90°C over a five and one-half hour period. TLC analysis showed the presence of some unreacted nitro­chlorobenzene.
  • the solution was cooled to 15 to 20°C and acidified by adding the 30 ml. of concentrated hydrochloric acid in 100 ml. of water during constant stirring.
  • the light colored solution was transferred to a separatory funnel followed by a 100 ml. toluene wash. On standing, the formed emulsion settled and the aqueous layer sepa­rated.
  • the organic layer was washed with 3 x 200 ml. por­tions of water then dried over magnesium sulfate.
  • Solvent was removed as described in Example 1 leaving a light orange colored liquid. Vacuum distillation of the liquid at 150 to 160°C under 0.05 mm. of mercury pressure provided 8.2 g. of 4-nitrochlorobenzene. There was obtained 212 g. of the di(nitroaromatic) compound in 74% yield based on recovered nitrochlorobenzene.
  • a 203 g. sample of the above compound was hydrogenated according to the procedure described in Example 1.
  • a 2.0 g. quantity of the 10% palladium on charcoal was used along with the 700 ml. of methanol.
  • the flask was charged to 4 kg/cm2 pressure of hydrogen and over a four and one-half hour period at ambient temperature (20°C) 2 kg/cm2 of hydrogen was consumed.
  • di(nitroaromatic) com­pound in accordance with formula (II) above wherein the diol residue was a polypropyleneoxy glycol having a molecular weight 2000, i.e., n 2, with the nitro groups in the ortho position on the aromatic ring.
  • the percent capping of the glycol was 90.4% based.
  • a 63.6 portion of the above di(nitroaromatic) compound was hydrogenated in the presence of 0.5 g. of 5% palladium on charcoal in 200 ml. of methanol using the procedure generally described above using a Parr shaker.
  • the reaction bottle was charged to 4 kg/cm2 pressure of hydrogen. Over a period of one hour and 15 minutes at ambient temperature (20°C), 1.7 kg/cm2 of hydrogen was consumed. After standing overnight, the pressure bottle was shaken for an additional hour but no further hydrogen uptake was noted.
  • Example 2 Using the apparatus and procedure set forth in Example 1, 200 g. (0.04 mole) of a 5000 molecular weight polypropyleneoxy-polyethyleneoxy capped triol containing 20% ethyleneoxy groups was mixed with 300 ml. of toluene under a steady stream of air. A 19.2 g. (0.12 mole) sample of 2-nitrochlorobenzene was added followed after five minutes by 12.2 g. (0.3 mole) of powdered sodium hydroxide. Stirring was carried out at room temperature. In ten minutes (at 26°C), the sodium hydroxide was all dissolved. After two hours of stirring at 24 to 28°C, the stirred solution was heated for a period of five hours at a temperature of 30 to 60°C.
  • a 100 g. sample of the tri(nitroaromatic) compound obtained above was hydrogenated in the presence of 1.0 g. of 5% palladium on charcoal in 150 ml. of methanol using the procedure previously described.
  • the reaction bottle was charged to 3.5 kg/cm2 of hydrogen. Over a period of shaking of four and one-half hours 0.8 kg/cm2 of hydrogen pressure was consumed. The bottle was repressured to 3.5 kg/cm2 but after one hour of shaking only 0.04 kg/cm2 of hydrogen was consumed.
  • reaction mixture was diluted with 100 ml. toluene, cooled to 10 to 15°C and acidified by adding 10 ml. of concentrated hydrochloric acid in 100 ml. water during gentle mixing.
  • the dark colored reaction mixture turned light orange.
  • the orange organic layer was separated and washed with 2 x 100 ml. portions of water and dried by storage over magnesium sulfate.
  • Solvent was removed in vacuo using a rotary evaporator under water pump pressure (10 mm. of mercury) leaving 45.0 g. of reddish colored viscous liquid; capping was 100 percent and gel permeation chromatography showed only one component.
  • a 10.8 g (0.0044 mole) portion of the above di(nitroaromatic) compound was hydrogenated in the presence of 0.5 g. of 3% palladium on charcoal in 100 ml. of methanol using the procedure generally described above using a Parr shaker.
  • the reaction bottle was charged to 3.5 kg/cm2 of hydrogen. Over a period of four hours (at 20°C) 0.25 kg/cm2 of hydrogen was consumed.
  • the mixture was cooled, diluted with 100 ml. of water and transferred to a separatory funnel along with 20 ml. of rinse toluene.
  • the separated organic layer was washed with dilute hydrochloric acid, followed by dilute sodium bicarbonate wash and finally with plain water.
  • the organic layer was dried over magnesium sulfate.
  • the product yield was 32 g. of a dark colored syrup which was 60% capped by the nitroaromatic residue.
  • An 84.1 g. (0.584 eq.) sample of a liquefied form of 4,4 ⁇ -methylenebis(phenyl isocyanate), in which a portion of the isocyanate groups have been converted to carbodiimide (I.E. 143), was added quickly to the beaker.
  • plaque was characterized by the following physical properties: Density 1.111 g./cc. Tensile strength (kg/cm2) 150 Tensile modulus (kg/cm2) 316 Elongation (%) 230 Hardness, Shore A 92 Die C Tear (kN/m) 59.5
  • a 500 ml. reaction flask was equipped with a stirrer, thermometer, addition funnel, and reflux condenser. The flask was charged with 10 g. (0.00874 eq.) of the di(aminoaromatic) compound described in Example 5 above, 1.5 g. of ethylene glycol, two drops of dibutyltin dilaurate, and 50 ml. of dimethylacetamide.
  • the isocyanate solution was added to the reaction flask during stirring and at the rate of 10 ml. per minute. Following this, the solution was heated at 145°C for 2 hours. Infrared analysis on aliquot samples showed the completion of reaction at the end of the 2 hour period by the absence of any isocyanate absorption.
  • reaction solution which contained the poly­urea-polyurethane resin at 20 percent by weight concentra­tion was transferred to a vacuum rotary evaporator.
  • Dimethylacetamide was removed under 10 mm. of mercury pressure and 80°C temperature until a solids concentration of at least 80 percent was reached.
  • DC-190 surfactant a silicone surfactant supplied by Dow-Corning Corporation, Midland, Michigan
  • Three separate films were prepared by casting three separate lots of concentrate solution respectively on (1) aluminum foil, (2) Mylar film, and (3) a glass plate. In each case a doctor knife adjusted to 0.38 mm height was used to apply the concentrate onto the substrate. This provided final films of about 0.25 mm.
  • the cast films on their respective substrates were dried according to the following cycle: (1) 30 minutes at ambient (20°C) temperature; (2) oven at 60°C for 3 minutes; and (3) vacuum oven (1 mm. of mercury pressure) at 30°C for 2 hours.
  • the aluminum foil provided the easiest film release, although both the glass and Mylar provided perfectly useful film release.
  • the polyurea-polyurethane film was characterized by the following physical properties: Density 1.201 g./cc. Tensile strength (kg/cm2) 48.5 Modulus (kg/cm2) 1014 Elongation (%) 30

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polyurethanes Or Polyureas (AREA)
EP87115677A 1986-10-27 1987-10-26 Blocage de polyols à l'aide d'amines aromatiques Expired - Lifetime EP0268849B1 (fr)

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US92325586A 1986-10-27 1986-10-27
US923255 1986-10-27
US07/035,121 US4847416A (en) 1986-10-27 1987-04-06 Capping of polyols with aromatic amines
US35121 1987-04-06

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EP0268849A2 true EP0268849A2 (fr) 1988-06-01
EP0268849A3 EP0268849A3 (en) 1989-12-13
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EP (1) EP0268849B1 (fr)
KR (1) KR920001652B1 (fr)
AU (1) AU595929B2 (fr)
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CA (1) CA1328468C (fr)
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EP0288825A2 (fr) * 1987-04-25 1988-11-02 Bayer Ag Polyamines aromatiques, leur procédé de préparation et leur utilisation pour la préparation de résines de polyuréthanes
US4885353A (en) * 1988-11-16 1989-12-05 Mobay Corporation Liquid isocyanate prepolymers
US4898971A (en) * 1989-01-23 1990-02-06 Mobay Corporation Liquid isocyanate prepolymers
US4914174A (en) * 1989-01-23 1990-04-03 Mobay Corporation Liquid isocyanate prepolymers
EP0363758A2 (fr) * 1988-10-12 1990-04-18 Bayer Ag Polyhydroxypolyamines aromatiques, leur procédé de préparation et leur utilisation pour la préparation de résines de polyuréthane
EP0371248A1 (fr) * 1988-11-03 1990-06-06 Miles Inc. Systèmes de polyurées préparés par le procédé de moulage réactif par injection
EP0370286A3 (en) * 1988-11-16 1990-06-06 Mobay Corporation Liquid isocyanate prepolymers
EP0431412A2 (fr) * 1989-12-06 1991-06-12 Bayer Ag Procédé pour la préparation d'élastomères de polyuréthane-urée résistant À  la chaleur
EP0433887A2 (fr) * 1989-12-22 1991-06-26 BASF Aktiengesellschaft Dérivés de polytétrahydrofurane à groupement aromatique terminal
EP0471966A2 (fr) * 1990-07-19 1992-02-26 Bayer Ag Procédé de préparation de polyéthers contenant des groupes aminophénoxy, composés obtenus par ce procédé et leur utilisation comme réactifs pour des polyisocyanates organiques
EP0517167A2 (fr) * 1991-06-04 1992-12-09 National Starch and Chemical Investment Holding Corporation Polyétheramines souples utilisés dans des compositions de résines époxyde
WO2005058994A1 (fr) 2003-12-16 2005-06-30 Bayer Materialscience, Llc Elastomeres de pulverisation de polyurethane-uree souple a resistance d'abrasion amelioree

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JP2577900B2 (ja) * 1987-02-18 1997-02-05 イハラケミカル工業 株式会社 ポリ尿素樹脂の製造方法
US4960950A (en) * 1988-03-28 1990-10-02 The Dow Chemical Company Formation of nitrophenyl ethers from polyols and nitroanisoles
US5219973A (en) * 1990-12-07 1993-06-15 Miles Inc. Polyurea rim systems
US5373028A (en) * 1991-08-20 1994-12-13 The Dow Chemical Company Polyurethane foams having reduced visible emissions during curing
US5510535A (en) * 1994-11-22 1996-04-23 Bayer Corporation Ether-linked amine-terminated polyethers and a process for their production
US5674943A (en) * 1995-02-14 1997-10-07 The Dow Chemical Company Polycarbonate compositions modified with a polyamine compound
US7101538B1 (en) * 2002-12-30 2006-09-05 Avon Products, Inc. Polyesteramine ingredient and use of same
US20110117156A1 (en) * 2004-05-27 2011-05-19 Arizona Chemical Company Compositions and articles containing an active liquid in a polymeric matrix and methods of making and using the same
DE102009040058A1 (de) 2009-03-06 2010-09-09 Bayer Materialscience Ag Verfahren zur Herstellung von Aminogruppen enthaltenden Polyoxyalkylenen
CN112250858B (zh) * 2020-08-31 2022-07-12 万华化学集团股份有限公司 一种制备阻燃聚合物多元醇的方法、应用及用其制成的聚氨酯泡沫塑料

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US4328322A (en) * 1979-12-03 1982-05-04 Polaroid Corporation Synthetic polymers by polyisocyanate polyaddition process
EP0257420A1 (fr) * 1986-08-21 1988-03-02 Bayer Ag Certains diisocyanates, procédé pour leur préparation et leur utilisation comme composant de synthèse pour la préparation de plastiques polyuréthaniques

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0288825A2 (fr) * 1987-04-25 1988-11-02 Bayer Ag Polyamines aromatiques, leur procédé de préparation et leur utilisation pour la préparation de résines de polyuréthanes
EP0288825A3 (fr) * 1987-04-25 1989-10-18 Bayer Ag Polyamines aromatiques, leur procédé de préparation et leur utilisation pour la préparation de résines de polyuréthanes
US5091582A (en) * 1987-04-25 1992-02-25 Bayer Aktiengesellschaft Process for the preparation of aromatic polyamines
EP0363758A3 (fr) * 1988-10-12 1991-05-02 Bayer Ag Polyhydroxypolyamines aromatiques, leur procédé de préparation et leur utilisation pour la préparation de résines de polyuréthane
EP0363758A2 (fr) * 1988-10-12 1990-04-18 Bayer Ag Polyhydroxypolyamines aromatiques, leur procédé de préparation et leur utilisation pour la préparation de résines de polyuréthane
EP0371248A1 (fr) * 1988-11-03 1990-06-06 Miles Inc. Systèmes de polyurées préparés par le procédé de moulage réactif par injection
US4885353A (en) * 1988-11-16 1989-12-05 Mobay Corporation Liquid isocyanate prepolymers
EP0370286A3 (en) * 1988-11-16 1990-06-06 Mobay Corporation Liquid isocyanate prepolymers
US4898971A (en) * 1989-01-23 1990-02-06 Mobay Corporation Liquid isocyanate prepolymers
US4914174A (en) * 1989-01-23 1990-04-03 Mobay Corporation Liquid isocyanate prepolymers
EP0431412A2 (fr) * 1989-12-06 1991-06-12 Bayer Ag Procédé pour la préparation d'élastomères de polyuréthane-urée résistant À  la chaleur
EP0431412A3 (en) * 1989-12-06 1992-02-19 Bayer Ag Process for the preparation of heat-resistant polyurethane-urea elastomers
EP0433887A2 (fr) * 1989-12-22 1991-06-26 BASF Aktiengesellschaft Dérivés de polytétrahydrofurane à groupement aromatique terminal
EP0433887B1 (fr) * 1989-12-22 1996-06-12 BASF Aktiengesellschaft Dérivés de polytétrahydrofurane à groupement aromatique terminal
EP0471966A2 (fr) * 1990-07-19 1992-02-26 Bayer Ag Procédé de préparation de polyéthers contenant des groupes aminophénoxy, composés obtenus par ce procédé et leur utilisation comme réactifs pour des polyisocyanates organiques
EP0471966A3 (en) * 1990-07-19 1992-04-29 Bayer Ag Process for the preparation of polyethers containing amino phenoxy groups, compounds from the process and their use as reactants for organic polyisocyanates
EP0517167A2 (fr) * 1991-06-04 1992-12-09 National Starch and Chemical Investment Holding Corporation Polyétheramines souples utilisés dans des compositions de résines époxyde
EP0517167A3 (en) * 1991-06-04 1993-01-13 National Starch And Chemical Investment Holding Corporation Flexible polyetheramines useful in epoxy compositions
WO2005058994A1 (fr) 2003-12-16 2005-06-30 Bayer Materialscience, Llc Elastomeres de pulverisation de polyurethane-uree souple a resistance d'abrasion amelioree

Also Published As

Publication number Publication date
DE3787871D1 (de) 1993-11-25
KR880005168A (ko) 1988-06-28
CA1328468C (fr) 1994-04-12
ES2059344T3 (es) 1994-11-16
BR8705702A (pt) 1988-05-31
EP0268849A3 (en) 1989-12-13
DE3787871T2 (de) 1994-03-10
EP0268849B1 (fr) 1993-10-20
AU7835387A (en) 1988-04-28
AU595929B2 (en) 1990-04-12
US4847416A (en) 1989-07-11
KR920001652B1 (ko) 1992-02-21

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